Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/54—Inks based on two liquids, one liquid being the ink, the other liquid being a reaction solution, a fixer or a treatment solution for the ink
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/40—Ink-sets specially adapted for multi-colour inkjet printing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
  • B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
  • B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
  • B41J2/01—Ink jet
  • B41J2/17—Ink jet characterised by ink handling
  • B41J2/175—Ink supply systems ; Circuit parts therefor
  • B41J2/17503—Ink cartridges
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/0023—Digital printing methods characterised by the inks used
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/023—Emulsion inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
  • C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/02—Printing inks
  • C09D11/10—Printing inks based on artificial resins
  • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/32—Inkjet printing inks characterised by colouring agents
  • C09D11/322—Pigment inks
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D11/00—Inks
  • C09D11/30—Inkjet printing inks
  • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes

Definitions

• the present invention relates to an ink-jet composition for ink-jet recording capable of forming an ink film excellent in both film strength and scratch resistance.
• an aqueous ink used in the printing field is mainly designed to target an absorbent substrate such as paper and synthetic paper, such as in Patent Documents 1 to 3.
• Such an aqueous ink is high in hydrophobicity, and it has been difficult to satisfy the printing quality required to unabsorbent plastic substrate such as polyethylene terephthalate (PET) and a vinyl chloride resin in the market; thus, a solvent ink and an UV-cured type ink has been often used.
• PET polyethylene terephthalate
• UV-cured type ink has been often used.
• demanded printing technique is to directly write to various unabsorbent substrates used in industrial application by using an aqueous ink that has small influence to the environment and is highly safe to workers.
• an aqueous ink including resin emulsion has been developed for the usage in the sign graphic field inside and outside houses targeted to an unabsorbent substrate such as vinyl chloride not conventionally used.
• Patent Documents 5, 6 and 7 relate to an ink for ink jet recording.
• an ink film is positioned on the surface of the substrate; thus, properties in film strength such as adhesiveness, solvent resistance, abrasion resistance, of those quality higher than when an absorbent substrate is used, are required, and furthermore, properties such as scratch resistance is required.
• the present invention has been made in view of the above problem, and a main object thereof is to provide an ink composition for ink-jet recording capable of forming an ink film excellent in both film strength and scratch resistance.
• the ink film excellent in both film strength and scratch resistant can be formed by using a silicone-acrylic resin emulsion in addition to a resin emulsion such as an acrylic resin emulsion, together as the resin emulsion in the ink composition, and further by setting the content of the resin emulsion ad the silicone-acrylic resin emulsion to be in the specific range; thereby, the present invention has been completed.
• the present invention provides an ink composition for ink-jet recording characterized by comprising: an aqueous solvent including water and water-soluble organic solvent; a coloring agent; a resin emulsion; and a surfactant; wherein the resin emulsion includes a silicone-acrylic resin emulsion and a resin emulsion other than the silicone-acrylic resin emulsion (hereinafter referred to as a second resin emulsion in some cases) ; a mass ratio of the resin emulsion to the coloring agent (content of the resin emulsion in terms of solid content / content of the coloring agent) is 1/5 or more and 15/1 or less; a mass ratio of the silicone-acrylic resin emulsion to the coloring agent (content of the silicone-acrylic resin emulsion in terms of solid content / content of the coloring agent) is 1/20 or more and 5/1 or less; and a mass ratio of the silicone-acrylic resin emulsion to the resin emulsion other than the silicone-acrylic resin
• both the silicone-acrylic resin emulsion and the second emulsion are included as the resin emulsion, and the content of these are in the specific range, and thus an ink film excellent in both film strength such as adhesiveness, solvent resistance, abrasion resistance, and water resistance, and scratch resistance, can be formed.
• the second resin emulsion preferably includes at least one kind of an acrylic resin, an urethane resin, an urethane-acrylic resin, a polyester resin, an acrylic polyester resin, a styrene acrylic resin, and an acrylic-vinyl chloride resin.
• the reason therefor is to allow the ink composition for ink-jet recording (hereinafter just referred to as an ink composition in some cases) to be capable of forming an ink film excellent in both film strength and scratch resistance.
• the water-soluble organic solvent includes alkanediols.
• the reason therefor is to allow the ink composition to be excellent in dispersion stability of the resin emulsion.
• the present invention provides an ink-set for ink-jet recording characterized by comprising: the above described ink composition for ink-jet recording; and a receiving solution containing a multivalent metal salt.
• the above described ink composition for ink-jet recording is included so as to obtain a printing excellent in both film strength and scratch resistance, and further excellent in image clarity.
• the present invention provides an ink cartridge characterized by comprising: a container for ink; and an ink composition stored in the container for ink; wherein the ink composition is the above described ink composition for ink-jet recording.
• the above described ink composition for ink-jet recording is included as the ink composition, so as to obtain a printing excellent in both film strength and scratch resistance.
• the present invention provides a method for producing a printing characterized by comprising a printing step of ejecting the above described ink composition for ink-jet recording by an ink-jet method.
• the above described ink composition for ink-jet recording is used in the printing step, so as to obtain a printing excellent in both film strength and scratch resistance.
• the present invention exhibits effects such as providing the ink composition for ink-jet recording capable of forming an ink film excellent in both film strength and scratch resistance.
• the present invention relates to an ink composition for ink-jet recording, an ink-set for ink-jet recording, an ink cartridge, and a method for producing a printing, using the ink composition.
• the ink composition for ink-jet recording, the ink-set for ink-jet recording, the ink cartridge and the method for producing a printing of the present invention are hereinafter explained.
• the ink composition for ink-jet recording of the present invention is characterized by comprising: an aqueous solvent including water and water-soluble organic solvent; a coloring agent; a resin emulsion; and a surfactant; wherein the resin emulsion includes a silicone-acrylic resin emulsion and a resin emulsion other than the silicone-acrylic resin emulsion; a content ratio of the resin emulsion to the coloring agent (content of the resin emulsion / content of the coloring agent) is 1/5 or more and 15/1 or less; a content ratio of the silicone-acrylic resin emulsion to the coloring agent (content of the silicone-acrylic resin emulsion / content of the coloring agent) is 1/20 or more and 5/1 or less; and a mass ratio of the silicone-acrylic resin emulsion to the resin emulsion other than the silicone-acrylic resin emulsion (content of the silicone-acrylic resin emulsion in terms of solid content / content of the resin emulsion
• both the silicone-acrylic resin emulsion and the second resin emulsion are included as the resin emulsion, and further, the content thereof are set to be in the specific range, so as to secure the ink-jet ejection properties and to achieve both the scratch resistance and the film strength such as adhesiveness, solvent resistance, abrasion resistance, and water resistance.
• the resin emulsion is the one in which a continuous phase is an aqueous solvent, and substances such as a resin included in the resin emulsion are dispersed in the aqueous solvent as fine particles.
• the resin can be dispersed in the ink composition for ink-jet recording by electrostatic repulsion and solid repulsion when the resin emulsion is formed.
• the resin emulsion has a characteristic of increasing viscosity and aggregating when the aqueous solvent which is generally continuous phase is decreased by factors such as evaporation and permeation; it has an effect of promoting fixation of coloring agents to a recording medium.
• the ink film presumably becomes excellent in the films strength thereby.
• the resin is included in the ink composition as an emulsion so as to allow the ink-jet ejection properties to be excellent.
• inclusion of the second resin emulsion other than the silicone-acrylic resin emulsion allows the ink composition to form an ink film excellent in film strength such as adhesiveness, solvent resistance, abrasion resistance, and water resistance to not only the absorbent substrate but also to the unabsorbent substrate.
• the silicone-acrylic resin included in the silicone-acrylic resin emulsion includes a polysiloxane structure, and the surface free energy is low; thus, when the ink composition film is formed by ink-jet ejecting the ink composition, there is a tendency the composition is likely to gather on the surface of the ink composition film. Accordingly, inclusion of the silicone-acrylic resin emulsion allows the ink composition to form an ink film with high content in the silicone-acrylic resin on the surface after the aqueous solvent of the ink composition film is dried and removed. Then, it is presumed that sliding property is given to the surface of such an ink film.
• the ink film even when materials such as a nail of the user using the printing touches the ink film, materials such as a nail is prevented from getting caught; scratch resistance becomes excellent.
• the substance that becomes in an emulsion state is used as the silicone-acrylic resin, so as to form an ink film capable of stably exhibiting the sliding properties.
• the silicone-acrylic resin included in the silicone-acrylic resin emulsion is the one including a structure comprising (meth)acrylic resin monomer such as poly (meth) acrylate, so as to be excellent in compatibility with the resin other than the silicone-acrylic resin (hereinafter referred to as a second resin in some cases) included in the second resin emulsion.
• the ink composition becomes excellent in sliding properties, and capable of forming an ink film excellent in scratch resistance and film strength such as adhesiveness, solvent resistance, abrasion resistance, and water resistance.
• the silicone-acrylic resin emulsion becomes more excellent in sustainability of the sliding properties; the ink film excellent in sustainability of scratch resistance can be formed compared to when, for example, just the silicone-based resin emulsion or the mixture of the silicone-based resin emulsion and the acrylic resin emulsion is used.
• the content of the second resin emulsion and the silicone-acrylic resin emulsion is in the above described ratio, and thus the ink composition can stably form an ink film that has a region with high content ratio of the second resin in inner side of the ink film, and the region with high content ratio of the above described silicone-acrylic resin in surface side of the ink film, as well as excellent film strength and scratch resistance.
• both the silicone-acrylic resin emulsion and the second emulsion are included as the resin emulsion, and the content of the both is set to be in the specific range, so as to allow the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the ink composition for ink-jet recording of the present invention includes an aqueous solvent, a coloring agent, a resin emulsion, and a surfactant.
• the resin emulsion includes the silicone-acrylic resin emulsion and a resin emulsion other than the silicone-acrylic resin emulsion.
• the content ratio of the resin emulsion to the coloring agent (content of the resin emulsion / content of the coloring agent) is 1/5 or more and 15/1 or less.
• the content ratio of the silicone-acrylic resin emulsion to the coloring agent is 1/20 or more and 5/1 or less.
• the lower limit of the content ratio of the resin emulsion to the coloring agent is 1/5 or more, preferably 1/3 or more, more preferably 1/2 or more, and particularly preferably 1/1 or more.
• the upper limit of the ratio is 15/1 or less, more preferably 12/1 or less, and particularly preferably 10/1 or less.
• the upper limit and the lower limit of the ratio is in the above described range, so as to allow the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the content ratio of the resin emulsion and the coloring agent, and the content ratio of the resin emulsions are indicated as the mass ratio.
• the content of the resin emulsion refers to the solid content of the resin emulsion; when just a resin is included as the resin emulsion, it refers to the content of the rein, and when the resin emulsion includes, for example, a resin and the other component such as an emulsifying agent, it refers to the total solid content of the resin and the other component.
• the lower limit of content ratio of the silicone-acrylic resin emulsion to the coloring agent is 1/20 or more, more preferably 1/10 or more, and further preferably 1/8 or more.
• the upper limit of the ratio is 5/1 or less, more preferably 3/1 or less, and further preferably 2/1 or less.
• the upper limit and the lower limit of the ratio are in the above described range, so as to allow the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the content ratio of the silicone-acrylic resin emulsion to the second resin emulsion is in the level that allows an ink film excellent in both film strength and scratch resistance to be obtained; for example, the lower limit thereof is 1/50 or more, and above all, is more preferably 1/40 or more, and further preferably 1/20 or more.
• the upper limit of the ratio is 1/2 or less.
• the upper limit and the lower limit of the ratio are in the above described range, so as to allow the ink composition to stably form an ink film that has a region with high content ratio of the second resin in inner side of the ink film and a region with high content ratio of the above described silicone-acrylic resin in surface side of the ink film.
• the silicone-acrylic resin emulsion includes a silicone-acrylic resin in an emulsion state inside the ink composition of the present invention.
• emulsion state refers to the state in which substances such as a resin included in the resin emulsion is dispersed as fine particles inside the ink composition.
• the resin in emulsion state has a characteristic of increasing viscosity and aggregating when an aqueous solvent which is generally continuous phase is decreased by factors such as evaporation and permeation, it can promote the fixation of the coloring agent to a recording medium.
• the silicone-acrylic resin is a copolymer comprising a repeated unit of (meth)acrylate (acrylic structural unit) and a repeated unit of siloxane represented by the below general formula (1) (siloxane-based structural unit) in the structure.
• silicone-acrylic resin may include the one containing both an acrylic resin including the acrylic structural unit as the main component, and a polysiloxane-based resin having a polysiloxane structure as the main skeleton.
• (meth)acryl means both “acryl” and “methacryl”.
• the silicone-acrylic resin may be the one in which an acrylic resin and a polysiloxane-based resin are bonded by covalent bonding; examples thereof may include a silicone-acrylic block copolymer in which the edges of acrylic resin and polysiloxane-based resin are bonded, a silicone-acrylic graft copolymer in which the acrylic resin in bonded as a side chain to the main skeleton of polysiloxane-based resin, an acrylic-silicone-based graft copolymer in which the polysiloxane-based resin is bonded as a side chain to the main skeleton of acrylic resin, and the one in which these copolymers are bonded.
• the silicone-acrylic resin being the above described copolymer allows the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the silicone-acrylic resin may include just one kind, and may include a mixture of two kinds or more.
• R 1 and R 2 are each independently a hydrogen atom, an alkyl group and a phenyl group with 1 to 4 carbon atoms; plurality of R 1 and R 2 may be the same and may be different from each other. Also, p is an integer of 2 or more.
• the acrylic resin includes the acrylic structural unit as a main component.
• included as a main component means to be included in the contents that is capable of giving silicone-acrylic resin compatibility with the second resin; in more specific, the content of the acrylic structural unit may be 50 mass% or more in the acrylic resin. In the present invention, the content of the acrylic structural unit in the acrylic resin is more preferably 75 mass% or more. The content being in the above described range allows the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the acrylic structural unit is the one capable of forming an ink film having desired scratch resistance and film strength, and preferably includes a structural unit derived from (meth)acrylate monomer having neither an acid group nor a hydroxyl group, as a main component.
• the reason therefor is to allow the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• included as a main component means to be included in the contents that is capable of giving the ink film both film strength and scratch resistance; in more specific, the content of the structural unit derived from (meth)acrylate monomer having neither an acid group nor a hydroxyl group in all the acrylic structural units may be 70 mass% or more, is more preferably 80 mass% or more, and further preferably 85 mass% or more. The content being in the above described range allows the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the upper limit of the content may be appropriately set in a range with which the ink film having desired scratch resistance and film strength can be formed;
• the acrylic structural unit may include, 100 mass% of, which means just the structural unit derived from (meth)acrylate monomer having neither an acid group nor a hydroxyl group, and it may be, for example, 99.9 mass% or less.
• the (meth)acrylate monomer having neither an acid group nor a hydroxyl group for example, the (meth)acrylate monomer having neither an acid group nor a hydroxyl group can be used.
• the (meth)acrylate monomer is preferably a substance such as methyl (meth) acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, octyl(meth)acrylate, nonyl(meth)acrylate, dodecyl(meth)acrylate, stearyl(meth)acrylate, cyclopentyl(meth)acrylate, cyclohexyl(meth)acrylate, and 2-methylcyclohexyl(meth)acrylate.
• the (meth)acrylate monomer being the above described (meth) acrylate monomer allows the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the acrylic structural unit may include an additional acrylate-based structural unit other than the structural unit derived from (meth)acrylate monomer having neither an acid group nor a hydroxyl group.
• a monomer configured in such an additional acrylic structural unit may be polymerizable monomer that can be polymerized with the (meth) acrylate monomer having neither an acid group nor a hydroxyl group; examples thereof may include the acid-group-containing monomer such as a carboxyl-group-containing monomer having methyleny unsaturated double bond such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and a carboxyl group; an amide-group-containing monomer such as (meth)acrylamide, and a hydroxyl-group-containing monomer having a hydroxyl group such as 2-hyddroxyethyl(meth)acrylate.
• the acid-group-containing monomer such as a carboxyl-group-containing monomer having methyleny unsaturated double bond such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, and a carboxyl group
• an amide-group-containing monomer such as (meth)acrylamide, and
• the acrylic resin may include an additional structural unit other than the acrylic structural unit.
• the monomer that can constitute such an additional structural unit may include other monomers such as vinyl acetate and styrene.
• the polysiloxane-based resin has a polysiloxane structure as a main skeleton.
• a structural unit (siloxane structural unit)configured in the polysiloxane structure is, for example, preferably the one including the structural unit represented by the formula (1) as the main component.
• the polysiloxane-based resin including the structural unit as the main component allows the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• included as the main component means to be included in the content capable of giving scratch resistance to the ink film; for example, 50 mass% or more of the structural unit represented by the formula (1) may be included in the polysiloxane-based resin.
• the content of the structural unit represented by the formula (1) in the polysiloxane-based resin is more preferably 75 mass% or more. The content being in the above described range allows the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the upper limit of the content may be appropriately set in the range the ink film having desired scratch resistance and film strength can be formed;
• the polysiloxane-based resin may include, 100 mass% of, which means just the structural unit represented by the formula (1), and it may be, for example, 99.9 mass% or less.
• R 1 and R 2 in the formula (1) are respectively a hydrogen atom, an alkyl group and a phenyl group with 1 to 4 carbon atoms; among them, an alkyl group with 1 to 4 carbon atoms is preferable, and particularly preferable is a methyl group: it is preferable that the polysiloxane-based resin is a polydimethylpolysiloxane-based resin having polydimethylsloxane as a main skeleton.
• the siloxane-based resin being in the structure allow the ink composition to be capable of forming an ink film excellent in scratch resistance.
• p if it is an integer of 2 or more; it is appropriately set according to a factor such as a weight average molecular weight.
• the polysiloxane-based resin may include an additional siloxane structural unit other than the structural unit represented by the formula (1), as the siloxane structural unit.
• a radical polymerizable siloxane structural unit having a radical polymerizable group may be included.
• the polysiloxane-based resin including the radial polymerizable siloxane structural unit allows polymerization with the (meth) acrylate monomer configured in the acrylic resin via the radical polymerizable group.
• the silicone-acrylic resin in which the acrylic resin and the polysiloxane-based resin are bonded can be easily obtained.
• the radical polymerizable silane compound that can constitute such a radical polymerizable siloxane structural unit may be the one bondable with the structural unit represented by the formula via a polysiloxane bonding.
• the content ratio of the acrylic structural unit and the siloxane-based structural unit (acrylic structural unit / siloxane structural unit) configured in the silicone-acrylic resin is to the extent that can form an ink film excellent in both film strength and scratch resistance, and is preferably in the range of 1/10 to 10/1.
• the content ratio being in the above described range allows the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the content of a silicon (Si) element in the silicone-acrylic resin may be to the extent that can form an ink film having desired scratch resistance; for example, the lower limit may be 1 mass% or more, is preferably 2 mass% or more, further preferably 3 mass% or more, and further more preferably 5 mass% or more.
• the upper limit of the content may be 50 mass% or less, is preferably 45 mass% or less, and further more preferably 40 mass% or less.
• the upper limit and the lower limit of the content being in the above described range allows the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the method for measuring the Si element content may be a method capable of accurately measuring the Si element content in the silicone-acrylic resin; for example, it may be measured by a method such as an ICP (Inductively Coupled Plasma) mass analysis method, and an XRF (X-ray Fluorescence Analysis).
• ICP Inductively Coupled Plasma
• XRF X-ray Fluorescence Analysis
• the molecular weight of the silicone-acrylic resin may be to the extent that can form an ink film having desired scratch resistance; for example, it may be in the range of 10000 to 10000000, and above all, is preferably in the range of 100000 to 500000.
• the molecular weight being in the above described range allows the ink composition to easily obtain an ink film excellent in both film strength and scratch resistance. Also, the emulsion state can be stably maintained in the ink composition thereby.
• the molecular weight indicates the weight average molecular weight Mw, which is the value measured by GPC (Gel Permeation Chromatography) (HLC-8120GPC from TOSOH CORPORATION, using N-methylpyrrolidone with the addition of 0.01 mol/litter lithium bromide as a dissolution medium, Mw377400, 210500, 96000, 50400, 206500, 10850, 5460, 2930, 1300, and 580 (those Easi PS-2 series from Polymer Laboratories) and Mw1090000 (from TOSOH CORPORATION) as polystyrene standard for calibration curve, and two columns of TSK-GEL ALPHA-MX as the measurement column.
• GPC Gel Permeation Chromatography
• the glass transition temperature of the silicone-acrylic resin may be to the extent that can form an ink film having desired scratch resistance; for example, it may be in the range of -50°C to 150°C, and above all, is preferably in the range of -20°C to 120°C, and in particular, preferably in the range of 0°C to 110°C.
• the glass transition temperature being in the above described range allows the ink composition to be capable of obtaining an ink film excellent in both film strength and scratch resistance.
• the glass transition temperature may be measured using a differential scanning calorimeter by a DSC method.
• the glass transition temperature may be measured by a differential scanning calorimeter (DSC) such as the differential scanning calorimeter "DSC-50" from Shimadzu Corporation.
• DSC differential scanning calorimeter
• a plurality of the glass transition temperature may be observed in some cases, but the main transition temperature with the larger endothermic amount may be adopted in the present invention.
• Tg may be adjusted depending on the factors such as the kind and the content of monomer configured in the resin.
• the method for forming the silicone-acrylic resin a known method may be used.
• a method of emulsion-polymerizing a polysiloxane macro monomer having a polymerizable group such as a (meth)acryloyl group, a vinyl group, a styryl group, an epoxy group, an alkoxysiryl group, and a mercapto group at the end, together with (meth) acrylate can be used.
• a method in which a polysiloxane-based resin having a polymerizable siloxane structural unit is formed as the polysiloxane-based resin, and then emulsion-polymerizing thereof together with (meth) acrylate monomer capable of constituting an acrylic resin, can be used.
• the lower limit of the average particle diameter of the silicone-acrylic resin emulsion in the ink composition may be, from the viewpoint of the dispersion stability of the silicone-acrylic resin emulsion and enabling the composition to form an ink film more excellent in film strength and scratch resistance, 10 nm or more, and above all, is preferably 30 nm or more, and further preferably 50 nm or more.
• the upper limit of the average particle diameter may be 500 nm or less, and above all, is preferably 300 nm or less, and further preferably 250 nm or less.
• the average particle diameter (average dispersion particle diameter) of the resin emulsion can be determined by dynamic light scattering.
• the dynamic light scattering is a method to measure a particle size utilizing the difference of light intensity distribution of diffractive scattering light depending on the particle sizes when lase light is illuminated to the particles; for example, the measurement can be conducted using micro track particle distribution measurement apparatus UPA from Nikkiso Co., Ltd., and a concentrated type particle size analyzer FPAR-1000 from OTSUKA ELECTRONICS Co.,LTD.
• the measurement may be conducted in the conditions: the measurement temperature of 25°C, the integration time of 3 minutes, and the wavelength of the laser used in the measurement being 660 nm, from the obtained data, the scattering intensity distribution is obtained, and the particle diameter with the highest frequency may be determined as the average particle diameter.
• the average particle diameter here is a volume average particle diameter.
• the silicone-acrylic resin emulsion includes the silicone-acrylic resin, and may include an additional component as required.
• Examples of such an additional component may include an emulsifying agent used for polymerizing the silicone-acrylic resin.
• the emulsifying agent the one generally use for emulsion polymerization can be used.
• Examples of commercially available products of the silicone-acrylic resin emulsion may include, but not limited to, CHALINE FE-502 (silicone-acrylic copolymer resin emulsion from Nissin Chemical co. , ltd.; ratio of acrylic structural unit / siloxane structural unit: 5/5; glass transition temperature: -20 to -10°C), CHALINE R-170BX (silicone-acrylic copolymer resin emulsion from Nissin Chemical co.
• the ratio of acrylic structural unit / siloxane structural unit indicates the mass ratio.
• the second resin emulsion is a resin emulsion other than the silicone-acrylic resin emulsion.
• Such a second resin emulsion if it is a resin other than a copolymer including both the acrylic structural unit and the siloxane-based structural unit in the structure, and capable of forming an ink film with desired film strength.
• an acrylic resin for example, an acrylic resin, a polystyrene resin, a polyester resin, a styrene-acrylic resin, a styrene resin, an acrylic-vinyl chloride resin, a vinyl chloride resin, a vinyl acetate resin, a vinyl chloride vinyl acetate copolymer resin, a polyethylene resin, an urethane resin, an acrylic polyester resin, an urethane-acrylic resin, an acrylamide resin, an epoxy resin, and the copolymer resin and mixture of these may be used.
• the second resin is preferably the resin such as an acrylic resin, an urethane resin, an urethane-acrylic resin, a polyester resin, an acrylic polyester resin, a styrene acrylic resin, and an acrylic-vinyl chloride resin, and above all, an acrylic resin is preferable.
• the second resin being the above described resin facilitates the adjustment of the monomer composition, the adjustment of the glass transition temperature (Tg), and the adjustment of the film formability and film resistance of the resin to allow the ink composition to be capable of forming an ink film excellent in film strength.
• the second resin may be used in just one kind, two or more kinds thereof may be mixed and used.
• the second resin the one generally used in an ink composition may be used.
• the acrylic resin if it includes a structural unit derived from (meth) acrylate monomer; for example, it may be the same as the acrylic resin described in the section "(1) Silicone-acrylic resin" above.
• urethane resin a generally known urethane resin used in an ink composition may be used.
• a copolymer of polyol having a hydroxy group as a side chain such as polyether polyol and polycarbonate polyol with diisocyanate such as hexamethylene diisocyanate and isophorone diisocyanate may be used.
• urethane-acrylic resin a generally known urethane-acrylic resin used in an ink composition may be used.
• a copolymer of acryl polyol including the acrylic structural unit as a main component with diisocyanate may be used.
• the content in the acrylic structural unit and the acryl polyol may be the same as that of the acrylic structural unit described in the section "(1) Silicone-acrylic resin" above.
• the acrylic-vinyl chloride resin includes both the structural unit derived from (meth)acrylate monomer (acrylic structural unit) and the structural unit derived from vinyl chloride (vinyl-chloride-based structural unit).
• the acrylic-vinyl chloride resin may be a random copolymer in which the acrylic structural unit and the vinyl-chloride-based structural unit are randomly copolymerized; however, a block copolymer in which the end of an acrylic resin having the acrylic structural unit as the main component and the end of a vinyl-chloride-based resin having a vinyl-chloride-based structural unit as a main component, are bonded together, an acrylic-vinyl-chloride-based graft copolymer in which a vinyl-chloride-based resin is bonded as a side chain to the main skeleton of the acrylic resin, a vinyl-chloride-acrylic graft copolymer in which an acrylic resin is bonded as a side chain to the main skeleton of a vinyl-chloride-based resin, and the one in which these copolymers are bonded together may be preferably used.
• the content in the acrylic structural unit and the acrylic resin may be the same as that of the acrylic resin described in the section "(1) Silicone-acrylic resin" above.
• the content of the vinyl-chloride-based structural unit included in the vinyl-chloride-based resin as a main component may be to the extent capable of achieving desired features such as film strength, and may be the same as the content of the acrylic structural unit in the acrylic resin described in the section "(1) Silicone-acrylic resin" above.
• the molecular weight of the second resin may be to the extent that can form an ink film with desired film strength; for example, it may be in the range of 10000 to 50000000, and above all, is preferably in the range of 100000 to 2000000.
• the molecular weight being in the above described range allows the ink composition to easily obtain an ink film excellent in film strength.
• the second emulsion can be stably maintained in emulsion state in the ink composition.
• the glass transition temperature of the second resin may be to the extent that can form an ink film with desired film strength; for example, it may be in the range of 20°C to 110°C, above all, is preferably in the range of 30°C to 90°C, and in particular, is preferably in the range of 40°C to 70°C.
• the glass transition temperature being in the above range allows the ink composition to easily form an ink film with favorably dried and excellent in film strength.
• Acid value of the second resin may be to the extent that can form an ink film with desired film strength; for example, it may be in the range of 0 mgKOH/g to 50 mgKOH/g, is preferably in the range of 0.01 mgKOH/g to 30 mgKOH/g, and above all, preferably in the range of 0.01 mgKOH/g to 25 mgKOH/g.
• the acid value being in the above range allows the ink composition to easily form an ink film excellent in film strength.
• the acid value in the present invention refers to the mass of potassium hydroxide (mg) required to neutralize the acid component included in 1 g of a sample (solid content of a resin); it may be measured from the method in conformity to the method described in JIS K 0070.
• an acid value may be adjusted by means such as the kind and the content of the monomer configured in the resin.
• the acid value may be, for example, adjusted by a feature such as the content of the structural unit derived from an acid-group-containing monomer such as (meth)acrylate in the second resin.
• the lower limit of the average particle diameter of the second resin emulsion in the ink composition may be, from the viewpoint of a feature such as dispersion stability of the second resin, 10 nm or more, and above all, is preferably 30 nm or more, and further preferably 50 nm or more.
• the upper limit of the average particle diameter may be 500 nm or less, and above all, is preferably 300 nm or less, and further preferably 250 nm or less.
• the second resin emulsion can have favorable ink-jet ejection properties, and can favorably form an ink film.
• the second resin emulsion includes the second resin, and may include an additional component as required.
• Examples of such an additional component may be in the same contents as those described in, for example, "(1) Silicone-acrylic resin" above.
• the aqueous solvent includes water and a water-soluble organic solvent.
• the aqueous solvent disperses or dissolves a coloring agent, a resin emulsion, and a surfactant.
• the content ratio of water and the water-soluble organic solvent in the aqueous solvent may be to the extent that can stably disperse materials such as the resin emulsion; for example, it may be in the range of 1/10 to 10/1, and above all, is preferably in the range of 3/10 to 10/3.
• the content ratio of water and the water-soluble solvent being in the above described range allows the ink composition to be capable of stably dispersing materials such as the resin emulsion.
• the content ratio indicates the mass ratio.
• the water-soluble organic solvent may be the one 10 parts by mass or more thereof can be dissolved in 100 parts by mass of water at 25°C under 1 pressure.
• an aqueous organic solvent may be used.
• the water-soluble organic solvent includes alkanediols having a structure in which two of a hydroxyl group is bonded to a chain saturated hydrocarbon, and above all, it is preferable that the alkanediols are included as the main component.
• the alkanediols are excellent in dispersing stability of the resin emulsion.
• the ink composition may be excellent in dispersing stability of the resin emulsion. Also, as the result, it is easy to increase the content ratio of the water-soluble organic solvent in the aqueous solvent.
• the boiling point of the alkanediols is usually higher than water; thus, it is easy for the ink composition to have less dry adhesion to a nozzle.
• included as a main component means to be included in the content with which the resin emulsion can be stably dispersed; for example, the content of the alkanediols in the water0soluble organic solvent may be 50 mass% or more, is preferably 60 mass% or more, more preferably 70 mass% or more, and further preferably 80 mass% or more.
• the upper limit of the content may be appropriately set in the range capable of obtaining desired dispersing stability; it may be included in 100 mass%, that means, the water-soluble organic solvent may include just the alkanediols, and the content may be appropriately adjusted to, for example, 95 mass% or less.
• the content of the alkanediols in the ink composition may be adjusted from the viewpoints such as the dispersing stability of the ink composition, inhibition of adhesion to a nozzle, and drying properties of the ink film.
• the water-soluble organic solvent in the ink composition when the content of the water-soluble organic solvent in the ink composition is 50 mass% or less, the water-soluble organic solvent may just include the alkanediols, that means the whole amount of the water-soluble organic solvent may be the alkanediols.
• the water-soluble organic solvent may include just the alkanediols, that means, the whole amount of the water-soluble organic solvent may be the alkanediols; however, the content of the alkanediols in the ink composition is preferably 50 mass% or more, and above all, preferably 10 mass% or more and 45 mass% or less, and in particular, preferably 35 mass% or more and 45 mass% or less.
• the upper limit and the lower limit of the content being in the above described range allows the ink composition to easily be excellent in features such as the dispersing stability of the ink composition, inhibition of adhesion to a nozzle, and drying properties of the ink film.
• the water-soluble organic solvent includes the alkanediols and a water-soluble organic solvent that is other than the alkanediols and has larger vapor pressure than that of the alkanediols added thereto, so as the ink composition to easily obtain an ink film with excellent drying properties.
• inclusion of the alkanediols in the specific amount or more allows the ink composition to easily be excellent in features such as dispersing stability and inhibition of adhesion to a nozzle.
• the difference of the vapor pressure from the alkanediols added thereto is preferably 100 Pa or more, and above all, preferably 150 Pa or more, and in particular, preferably 200 Pa or more.
• the vapor pressure (Pa) indicates the saturated vapor pressure at 50°C.
• the vapor pressure of propylene glycol is 133 Pa
• the vapor pressure of 3-methoxy-1-butanol is 460 Pa.
• the difference from the vapor pressure of the alkanediols added thereto refers to the difference from the vapor pressure of the alkanediols with the highest vapor pressure.
• the alkanediols may be the one having a structure in which two of a hydroxyl group is bonded to a chain saturated hydrocarbon.
• the alkanediols are preferably alkanediols having 6 or less carbon atoms such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, isobutylene glycol, triethylene glycol, 1,2-butandiol, 1,3-butandiol, 1,4-butandiol, 1,2-pentandiol, 1,2-hexandiol, 1,5-pentandiol, 1,6-hexanediol, 2-methyl-2,4-pentandiol, 3-methyl-1,3-butandiol, and 3-methyl-1,5-pentandiol.
• the alkanediols facilitates the maintenance of the dispersing stability of the resin emulsion while having less adhesion to a nozzle.
• the boiling point of the water-soluble organic solvent may be to the extent capable of forming an ink film; for example, it is preferably 280°C or less, and above all, preferably in the range of 150°C to 250°C.
• the boiling point in the above described range allows the ink composition to easily have less dry adhesion to a nozzle, and be favorable in ejection properties.
• the upper limit of the boiling point in the above described range allows the ink film of the ink composition to be easily dried and be excellent in film strength such as water resistance and adhesiveness.
• the content of the water-soluble organic solvent of which boiling point is 240°C or more in the ink composition is preferably less than 5 mass%.
• the content of the water-soluble organic solvent may be to the extent that can stably disperse or dissolve each component such as the resin emulsion.
• the content in the ink composition may be 80 mass% or less, is preferably 70 mass% or less, and above all, preferably 60 mass% or less, in particular, preferably in the range of 0.1 mass% to 50 mass%, and above all, preferably in the range of 1 mass% to 40 mass%.
• the content of the water-soluble organic solvent in the above described range allows the ink composition to easily obtain an ink film excellent in drying properties.
• the content of the water-soluble organic ink in the ink composition is, from the viewpoint of dispersing stability, preferably 80 mass% or less, and from the viewpoint of inhibition of adhesion to a nozzle, preferably 5 mass% or more.
• the content of the water-soluble organic ink in the ink composition is, preferably 15 mass% or more and 70 mass% or less, and above all, preferably 25 mass% or more and 60 mass% or less.
• the upper limit and the lower limit of the content of the water-soluble organic solvent in the above described range allows the ink composition to be excellent in dispersing stability and have less adhesion to a nozzle.
• the content of the water-soluble organic solvent in the ink composition may be, from the viewpoints of both the formation of an ink film excellent in drying properties and inhibition of adhesion to a nozzle, 15 mass% or more and 80 mass% or less, is preferably 20 mass% or more and 70 mass% or less, and above all, preferably 25 mass% or more and 60 mass% or less, in particular, preferably 30 mass% or more and 60 mass% or less, and particularly above all, preferably 40 mass% or more and 60 mass% or less.
• the content of the aqueous solvent may be to the extent that can stable disperse or dissolve each component such as the resin emulsion.
• the content of the water-soluble organic solvent and aqueous solvent may be respectively referred to as just the content of the water-soluble organic solvent and the content of the aqueous solvent.
• the surfactant is to adjust the surface tension of the ink composition and to adjust the wet spread of the ink composition to a recording medium where the ink composition is ink-jet ejected.
• a generally known surfactant used in an ink composition may be used.
• the surfactant is preferably a polysiloxane-based surfactant of which weight average molecular weight is in the range of 1000 to 30000 since it has an excellent effect of reducing the surface tension that allows the ink composition to be excellent in temporal stability of surface tension and excellent in printing suitability.
• the polysiloxane-based surfactant has polysiloxane as a main skeleton.
• to have polysiloxane as a main skeleton may refer to, in particular, to have the siloxane structural unit represented by the below formula (2) as a main component.
• R 3 and R 4 each independently represents a hydrogen atom, an alkyl group with 1 to 4 carbon atoms and a phenyl group; a plurality of R 3 and R 4 may be the same and may be different from each other. Also, q is an integer of 2 or more.
• q if it is an integer of 2 or more, and it is appropriately set according to factors such as the weight average molecular weight.
• R 3 and R 4 in the formula (2) may be the same as R 1 and R 2 described in the section "1. Silicone-acrylic resin emulsion" above.
• the siloxane structural unit represented by the formula (2) is included in the polysiloxane-based surfactant as a main component.
• included as a main component means to be included in the content capable of giving the ink composition an effect of reducing surface tension; for example, the structural unit represented by the formula (2) may be mass% or more in the polysiloxane-based surfactant.
• the content of the structural unit represented by the formula (2) in the polysiloxane-based surfactant is more preferably 75 mass% or more. The content in the above described range allows the polysiloxane-based surfactant to have an excellent effect of reducing surface tension.
• polysiloxane-based surfactant if it has the siloxane structural unit as the main component; however, the one having a polyether group, that is, a polyether group modified polysiloxane-based surfactant is preferable.
• a polyether group modified polysiloxane-based surfactant is preferable.
• the inclusion of the polyether group easily allows the polysiloxane-based surfactant to have water-solubility.
• polyether group may include an alkylene oxide containing group; above all, an ethylene oxide containing group and a propylene oxide containing group are preferable, and in particular, an ethylene oxide containing group is preferable.
• an alkylene oxide containing group above all, an ethylene oxide containing group and a propylene oxide containing group are preferable, and in particular, an ethylene oxide containing group is preferable.
• the polyether group facilitates the polysiloxane-based surfactant to have water-solubility.
• polyether group modified polysiloxane-based surfactant if it has the polyether group; an example thereof is the one having a polyether group containing structural unit in which one of a silicon atom at one end or both ends of the polysiloxane structure, and the side chain of the polysiloxane structure, that is R 3 and R 4 in the siloxane structural unit represented by the formula (2), is substituted with a polyether group.
• the weight average molecular weight of the polysiloxane-based surfactant if it is in the range of 1000 to 30000; it is preferably in the range of 2000 to 20000, and above all, preferably in the range of 3000 to 10000.
• the molecular weight in the above described range allows the ink composition of the present invention to be excellent in wet spreadability.
• Examples of the commercially available product of the polysiloxane-based surfactant may include FZ-2122, FZ-2110, FZ-7006, FZ-2166, FZ-2164, FZ-7001, FZ-2120, SH 8400, FZ-7002, FZ-2104, 8029 ADDITIVE, 8032 ADDITIVE, 57 ADDITIVE, 67 ADDITIVE, 8616 ADDITIVE (all from The Dow Chemical Company), KF-6012, KF-6015, KF-6004, KF-6013, KF-6011, KF-6043, KP-104, 110, 112, 323, 341 (all from Shin-Etsu Chemical Co., Ltd.), BYK-300/302, BYK-301, BYK-306, BYK-307, BYK-320, BYK-325, BYK-330, BYK-331, BYK-333, BYK-337, BYK-341, BYK-342, BYK-344, BY
• the polysiloxane-based surfactant is preferably water-soluble; if it is water-soluble, the deterioration of ejecting properties due to deposition of the polysiloxane-based surfactant to the surface of the ink composition and to the surface of the member in an ink-jet head that causes repelling of the ink composition can be inhibited.
• water-soluble means 0.1 parts by mass or more can be dissolved in 100 parts by mass of water at 25°C under 1 pressure.
• the method for adjusting the level of water-solubility of the polysiloxane-based surfactant may be adjusted by the factors such as the kind and number of the polyether group, and the molecular weight of the polysiloxane-based surfactant.
• an additional surfactant other than the above described polysiloxane-based surfactant may be used.
• the additional surfactant may include an anion-based surfactant, a non-ionic surfactant, a fluorine-based surfactant, an alkylene-oxide-modified acetylene-glycol-based surfactant, and an alkylene-oxide-non-modified acetylene-glycol-based surfactant.
• alkylene-oxide-non-modified acetylene-glycol-based surfactant may include 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,5-dimethyl-1-hexyne-3-ol, 3-methyl-1-butyne-3-ol, 3-methyl-1-pentyne-3-ol, 3-hexyne-2,5-diol, and 2-butyn-1,4-diol.
• products such as Sufynol61, 82, and 104 (all from Air Products and Chemicals, Inc.) may be used.
• alkylene-oxide-modified acetylene-glycol-based surfactant may include Sufynol420, 440, 465, 485, TG, 2502, Dynol604, 607 (all from Air Products and Chemicals, Inc.), Sufynol SE, MD-20, OlfineE1004, E1010, PD-004, EXP4300, PD-501, PD-502, SPC (all from Nissin Chemical Co., Ltd.), Acetynol EH, E40, E60, E81, E100, and E200 (all from Kawaken Fine Chemicals Co., Ltd.).
• anion-based surfactant examples include EMAL, LATEMUL, NEOPELEX, DEMOL (all an anion-based surfactant from Kao Corporation.), SUNNOL, LIPOLAN, LIPON, LIPAL (all an anion-based surfactant from Lion Corporation.), NOIGEN TM , EPAN TM , SORGEN TM (all non-ionic surfactant from DKS Co.
• EMULGEN 320P (all an anion-based surfactant), EMULGEN 320P, EMULGEN 350, EMULGEN 430, EMULGEN 130K, EMULGEN 150 from Kao Corporation., NOIGEN TM TDS-120, NOIGEN TM TDS-200D, NOIGEN TM TDS-500F from DKS Co.
• BLAUNON SR-715 BLAUNON SR-720, BLAUNON SR-730, BLAUNON SR-750, BLAUNON EN-1520A, BLAUNON EN-1530, BLAUNON EN-1540 from AOKI OIL INDUSTRIAL Co., Ltd., Newcol TM 2310, Newcol TM 2320, Newcol TM 2327, Newcol TM 1545, Newcol TM 1820 from NIPPON NYUKAZAI CO., LTD., and NIKKOL BPS20, NIKKOL BPS30 from Nikko Chemicals Co., Ltd. (all non-ionic surfactant).
• These surfactant may be used solely and two or more kinds thereof may be used together.
• the content of the surfactant if it has desired wet spreadability; for example, in the ink composition, the content is preferably in the range of 0.01 mass% to 10.0 mass%, more preferably in the range of 0.1 mass% to 5.0 mass%, further preferably in the range of 0.3 mass% to 5.0 mass%, and more preferably from 0.5 mass% to 3.0 mass% or less.
• the content in the above described range allows the ink composition to have favorable wet spreadability, and the dot diameter of the impact of the ink composition to a recording medium can be widened. Also, an ink film can be excellent in both film strength and scratch resistance thereby.
• coloring agent in the present invention a generally known coloring agent used in an aqueous ink can be used; for example, a pigment such as an organic pigment and an inorganic pigment can be used.
• the pigment may be a pigment dispersion in which the pigment is dispersed in an aqueous solvent by a material such as a surfactant for pigment dispersion and a dispersing agent, and it may be included as a hydrophilic group modified self-dispersing pigment dispersion on the pigment surface.
• the content of the coloring agent if it is capable of forming a desired image and may be appropriately adjusted. In specific, it may depend on the kind of the coloring agent, but the content to the whole amount 100 mass% of the ink composition is preferably in the range of 0.05 parts by mass to 20 parts by mass, and more preferably in the range of 0.1 parts by mass to 10 parts by mass. The content in the above described range allows the balance between the dispersing stability and the tinting strength of the coloring agent to be excellent.
• the ink composition of the present invention comprises an aqueous solvent, a coloring agent, a resin emulsion, and a surfactant, and may further include an additional component as required.
• Examples of the additional component may include a penetrant, a humectant, a preservative, an antioxidant, a conductivity adjuster, a pH adjuster, a viscosity adjuster, an antifoamer, and a deoxidizing agent.
• I fit is a method that allows the each component to be dispersed or dissolved in a solvent.
• Examples of the preparation method may include a preparation method in which a pigment dispersion is added to the aqueous solvent as the coloring agent and dispersed and then the resin emulsion, the surfactant and an additional component as required are added thereto, a preparation method in which the coloring agent and a dispersing agent are added to the aqueous solvent to be dispersed, and then the resin emulsion, the surfactant and an additional component as required are added thereto, and a preparation method in which the coloring agent, the resin emulsion, the surfactant and an additional component as required are added to the aqueous solvent and then the coloring agent is dispersed.
• the ink-set for ink-jet recording of the present invention is characterized by comprising the above described ink composition for ink-jet recording, and a receiving solution containing a multivalent metal salt.
• the above described ink composition for ink-jet recording is included and thus a printing excellent in both film strength and scratch resistance as well as in image clearness can be obtained.
• the ink-set for ink-jet recording of the present invention comprises the above described ink composition for ink-jet recording and a receiving solution.
• the ink composition may be in the same contents of those described in the section "A. Ink composition for ink-jet recording" above; thus, the descriptions herein are omitted.
• the receiving solution used in the present invention contains a multivalent metal salt.
• the multivalent metal salt if it improves the fixity of the ink composition on a recording medium and a metal salt of divalent or more configured by a pair of a multivalent metal ion and the negative ion that is a pair of the multivalent ion; it may be an inorganic metal salt and may be an organic acid metal salt. It is preferable that such a multivalent metal salt is one kind o more selected from a group consisting of calcium salt, magnesium salt, nickel salt, aluminum salt, boron salt, and zinc salt. The reason therefor is to inhibit the bleeding of an ink and the bleeding of a color between different colors (among inks) to obtain an image excellent in image clearance without printing nonuniformity or a missing white part.
• the metal salt of divalent or more may be used in one kind solely, and may be used in combination of two or more kinds.
• the receiving solution contains the multivalent metal salt, and usually include a solvent, a resin component and a surfactant.
• it may include a material such as a penetrant, a preservative, an antioxidant, conductivity adjuster, a pH adjuster, a viscosity adjuster, an antifoamer, and a deoxidizing agent, as required.
• a material such as a penetrant, a preservative, an antioxidant, conductivity adjuster, a pH adjuster, a viscosity adjuster, an antifoamer, and a deoxidizing agent, as required.
• the surfactant the one same as that described in the section "A. Ink composition for ink-jet recording" above may be used.
• the solvent, the resin component, and the other additive may be those generally used in a receiving solution.
• the ink-set of the present invention includes the ink composition and a receiving solution, and may include an additional constitution as required.
• the ink cartridge of the present invention is characterized by comprising a container for ink, an ink composition stored in the container for ink, wherein the ink composition is the above described ink composition for ink-jet recording.
• the above described ink composition for ink-jet recording is included as the ink composition so as to obtain a printing excellent in both film strength and scratch resistance.
• the ink cartridge of the present invention includes a container for ink and an ink composition.
• the ink composition may be in the same contents as those described in the section "A. Ink composition for ink-jet recording" above; thus, the descriptions herein are omitted.
• the container for ink is to store the ink composition.
• Such an ink container may be the one that can be used in an ink-jet printer; there are no particular limitations on the container.
• the shape, structure, size, and material thereof may be appropriately selected according to a purpose; suitable examples thereof may include the one having an ink bag formed by an aluminum laminate film and a resin film.
• An example thereof may be a bag-shape container such as an ink bag formed by layering two pieces of an aluminum laminate films bonded by means such as heat sealing.
• the ink container may be the one having an opening for taking out an ink to eject the ink composition during usage.
• At least one thereof is included in the ink cartridge of the present invention, and may be two or more thereof may be included.
• the kind of the ink composition stored in each ink container may be the same and may be different from each other.
• examples of the combination of the ink composition when the kind is different may include a combination of ink compositions of which kind of the coloring agent included in the ink composition is different and that can form an ink film with different colors.
• the ink cartridge of the present invention includes the container for ink and the ink composition, and may include an additional constitution as required. It is particularly preferable that the ink cartridge is used by installing thereof to an ink-jet recording device in removable state.
• the additional constitution may be the one generally used in an ink cartridge, and examples thereof may include an outside frame covering the ink container.
• Such an outside frame may be the one general in an ink cartridge.
• the outside frame may include an opening where the opening for taking out an ink arranged in the ink container is exposed.
• the method or producing a printing of the present invention is characterized by comprising a printing step of ejecting the above described ink composition for ink-jet recording by an ink-jet method.
• the above described ink composition for ink-jet recording is used in the printing step so as to obtain a printing excellent in both film strength and scratch resistance.
• the method for producing a printing of the present invention includes the printing step.
• the printing step is a step of ejecting the above described ink composition for ink-jet recording by an ink-jet method.
• the ink-jet method in this step may be any ink-jet method such as in piezo type, thermal type, and static type.
• the piezo type ink-jet method is preferably from the points an aggregate is not easily generated and it is excellent in ejecting stability.
• the ink-jet head (recording head) in piezo type uses a piezoelectric vibrator as a pressure generating element, and ejects an ink drop by deforming the piezoelectric vibrator to pressurize or decompress the pressure room.
• the ink drop amount of the ink composition to be ejected by the ink-jet method in the present step may be appropriately set according to factors such as application and color, and it may be in the range of 0.5 pl to 30 pl.
• the recording medium to which the ink composition is ejected in the present step if it can be printed using the ink composition both an absorbent substrate and an unabsorbent substrate may be used.
• Exemplifications of the absorbent substrate may include uncoated paper such as woody paper, medium quality paper, and wood free paper; coated paper such as coated paper, art paper, and cast paper; cotton, artificial fiber textile, silk, hemp, fabric, nonwoven fabric, and leather.
• unabsorbent substrate may include but not is limited to a polyester-based resin, a polyethylene-based resin, a polypropylene-based resin, a vinyl-chloride resin, a polyimide resin, and the aforementioned resin containing synthetic paper, a metal, a metal foil coated paper, glass, synthetic rubber, and natural rubber.
• the recording medium is preferably the unabsorbent substrate, and among them, a substrate made of a resin such as a polyester-based resin, a polyethylene-based resin, a propylene-based resin, a vinyl chloride resin, a polyimide resin, and the aforementioned resin containing synthetic paper is preferable, and a substrate made of a vinyl chloride resin is more preferable.
• a substrate made of a resin such as a polyester-based resin, a polyethylene-based resin, a propylene-based resin, a vinyl chloride resin, a polyimide resin, and the aforementioned resin containing synthetic paper is preferable, and a substrate made of a vinyl chloride resin is more preferable.
• the production method of the present invention includes the printing step and may include an additional step as required.
• Examples of the additional step may include a receiving solution placing step of placing the receiving solution on the recording medium before the printing step, and a drying step of drying and removing the aqueous solvent included in the ink composition film of the ink composition by means such as heating the recording medium after the printing step to form an ink film.
• the receiving solution used in the receiving solution placing step may be in the same contents as those described in the section "B. Ink-set for ink-jet recording" above; thus, the descriptions herein are omitted.
• the method for placing the receiving solution on the recording medium if it is a method in which the receiving solution can be placed on the recording medium before the printing step is conducted.
• Examples thereof may include a method using means such as a spray method, a coater method, an ink-jet method, a gravure method, and a flexo method.
• the forming method is preferably a method in which the receiving solution is placed on the recording medium using an ink-jet method.
• the point to place the receiving solution may be the point where the improvement in the fixity of the ink composition film ink-jet ejected in the printing step is possible; for example, it may be the whole surface of the recording medium, and may be in a pattern shape in which the ink composition of the recording medium overlaps with the point where the ink-jet is ejected in planar view.
• word printing is possible using means such as an ink-jet method as the method for placing the receiving solution, on the same point as the point where word printing of the ink composition is conducted in the printing step.
• the amount of the receiving solution per a unit area placed on the recording medium can be appropriately set according to factors such as the kind of the receiving solution.
• the printing produced by the method for producing a printing of the present invention includes a recording medium and an ink film formed by using the ink composition formed on the recording medium.
• the ink film formed on the recording medium is a dry film of the ink composition film formed by using the ink composition, which includes the solid content of the ink composition and the aqueous solvent thereof is dried and removed.
• the solid content indicates all the components in the ink composition other than the aqueous solvent.
• the present invention is not limited to the embodiments.
• the embodiments are exemplifications, and any other variations are intended to be included in the technical scope of the present invention if they have substantially the same constitution as the technical idea described in the claim of the present invention and offer similar operation and effect thereto.
• numeric values for each component in Tables 1 to 4 indicates parts by mass.
• the values for the pigment, the dispersing agent, the second resin emulsion, the silicone-acrylic resin emulsion, and the surfactant indicates parts by mass of the solid content in each component.
• the used pigment dispersion, second resin emulsion, silicone-acrylic resin emulsion, surfactant, and water-soluble organic solvent were as follows.
• the pigment dispersing resin was prepared by the below method.
• the obtained pigment dispersing resin of 2.5 g and N,N-dimethylaminoethanol of 0.6 g were dissolved in an ion exchanged water of 80 g, carbon black of 15.0 g and an antifoamer ("Sufynol 104PG" from Air Products and Chemicals, Inc.) of 0.05 g were added thereto, the product was dispersed by a paint shaker using zirconia beads to obtain pigment dispersion A-1.
• pigment dispersion A-2 a self-dispersing pigment dispersion Cab-O-Jet 400 (from Cabot Corporation.) was used.
• pigment dispersion A-3 a self-dispersing pigment dispersion SENSIJET ULTRA Black (from Sensient Technologies Corporation) was used.
• Pigment dispersion A-4, A-5, and A-6 were obtained in the same manner as for pigment dispersion A-1 except that C.I. pigment yellow 155, C.I. pigment red 122, C.I. pigment blue 15:3 were respectively used instead of carbon black.
• a reactive surfactant product name: LATEMUL PD-104 from Kao Corporation.
• 0.01 g of potassium persulfate, and 200 g of pure water were agitated and mixed at 70°C. After that, the prepared pre-emulsion was dropped into the flask for 3 hours.
• the product was heated and matured at 70°C for further 3 hours and then cooled down, the pH was adjusted to be 8 by N,N-dimethyl ethanolamine, filtrated by #150 mesh (from Japan Fabric) to obtain 500 g of second resin emulsion B-1 (solid content of 30 mass%, glass transition temperature of 64°C, acid value of 7 mgKOH/g, and average particle diameter of 120 nm) .
• RIKABOND TM SU100 urethane acrylic resin from Japan Coating Resin co., ltd.; average particle diameter of 84 nm, Tg of 48°C, and acid value of 16 mgKOH/g was used.
• VINYBLAN TM 701NL50 (vinyl chloride acrylic resin from Nissin Chemical co., ltd.; average particle diameter of 70 nm, Tg of 57°C, and acid value of 50 mgKOH/g) was used.
• VINYBLAN TM 701RL50S vinyl chloride acrylic resin from Nissin Chemical co., ltd.; average particle diameter of 100 nm, Tg of 26°C, and acid value of 50 mgKOH/g was used.
• CHALINE LC190 from Nissin Chemical co., ltd. ; average particle diameter of 200 nm to 300 nm, Tg of 90°C to 110°C, and ratio of acrylic structural unit / siloxane structural unit of 1/9 as silicone acrylic resin emulsion C-1
• CHALINE FE 203N from Nissin Chemical co., ltd.; average particle diameter of 200 nm to 300 nm, Tg of 50°C, and ratio of acrylic structural unit / siloxane structural unit of 5/5) as C2
• MOWINYL 7110 from Nissin Chemical co., ltd.; Tg of 30°C and acid value of 15 mgKOH/g
• VONCOAT SA6360 from DIC Corporation; average particle diameter of 150 nm and Tg of 21°C) as C-4, were used.
• the silicon content measured by an XRF measurement was 20.0 mass% in C-1, 11.2 mass% in C-2, 2.0 mass% in C-3, and 0.1 mass% in C-4.
• PG propylene glycol
• 1,2-pentandiol 1,2-pentandiol
• 1,3-propanediol 1,3-PD
• glycerin Gly
• 1,6-hexanediol 1,6-HD
• 3-methoxy-1-butanol MB
• PG water-soluble organic solvent
• 1,2-PD 1,3-PD
• 1,6-HD alkanediols
• Example 3 is a Reference Example.
• Example 1 The ink compositions obtained in Examples and Comparative Examples were respectively filled into an ink-jet printer in which an ink-jet head having piezo element was installed under the environment of 25°C, solid printing with coverage rate of 100% was conducted to a polyvinyl chloride sheet (MD-5 from Metamark) while heating the sheet to 40°C, and the printing was dried for 5 minutes on a heater heated to 80°C.
• an ink-jet head having piezo element was installed under the environment of 25°C
• solid printing with coverage rate of 100% was conducted to a polyvinyl chloride sheet (MD-5 from Metamark) while heating the sheet to 40°C, and the printing was dried for 5 minutes on a heater heated to 80°C.
• MD-5 polyvinyl chloride sheet
• ⁇ E a2 ⁇ a1 2 + b2 ⁇ b1 2 + L2 ⁇ L1 2 0.5 .
• the values of a2, b2, and L2 are the Lab values after the test, and the values of al, bl, and L1 are the Lab values before the test.
• cellophane tape was pressed and adhered to dry-treated ink film surface and the state of the ink film when peeled off at 90° was visually evaluated.
• evaluation basis was as follows; evaluations ⁇ and ⁇ are in the practicable range:
• the ink composition was ejected from all nozzles using an ink-jet head having a piezo element, and then nozzle patterns were printed after the carriage was brought into waiting state once to evaluate the number of nozzles having ejection failure and the reinstatement level of the ejection property through a cleaning step.
• a cleaning solution with the composition of the ink composition in Example 1 excluding the pigment and the resin emulsion was used.
• the evaluation basis was as follows; evaluations other than ⁇ are in the practicable range.
• the cleaning step is an operation of wiping off the ink composition and air bubble adhered to a nozzle surface by hand using nonwoven fabric permeated with the cleaning solution.
• the measurement of the surface tension was conducted using a plate type surface tension meter (CBVP-Z from Kyowa Interface Science, Inc.) under the environment of 25°C ⁇ 0.5°C.
• CBVP-Z plate type surface tension meter
• Example 2 From the comparison of Example 2 to Examples such as Example 15, it was confirmed that the ink film became excellent in drying properties by using just the one having a boiling point of less than 280°C as the water-soluble organic solvent.
• the receiving solution was printed by the following method, and then onto where the receiving solution was printed, a printing in which the ink in combination of the ink compositions of Examples 1, 21, 22, and 23 (the ink containing dispersion A-1 of carbon black, dispersion A-4 of C.I. pigment yellow 155, dispersion A-5 of C.I. pigment red 122, and dispersion A-6 of C.I. pigment blue 15:3) was formed, and the tests for abrasion resistance, drying properties, solvent resistance, printing image quality B and printing image quality C on the printing were conducted. The results are shown in the below Table 5.
• condition "a” is the evaluation result without printing of receiving solution
• condition "b” is the evaluation result with printing of receiving solution
• Printing image quality B and C were evaluated by the method shown below.
• a receiving solution was obtained by blending 1.7 parts by mass of magnesium propionate, 33.0 parts by mass of 1,2-pentandiol, 0.5 parts by mass of SILFACE SAG503A (surface tension adjuster from Nissin Chemical co., ltd.), 4.0 parts by mass (converted to solid content) of SUPER FLEX620 (acrylic resin emulsion from TAISEI FINE CHEMICAL CO, .LTD.), and 60.8 parts by mass of ion exchanged water.
• SILFACE SAG503A surface tension adjuster from Nissin Chemical co., ltd.
• SUPER FLEX620 acrylic resin emulsion from TAISEI FINE CHEMICAL CO, .LTD.
• the receiving solution prepared by the above described method was filled into an ink-jet printer in which an ink-jet head having piezo element was installed in the same manner as in "(1) Water resistance” above, the same image as the image to be printed with the ink composition was printed to a polyvinyl chloride sheet (MD-5 from Metamark), and then the ink composition was printed onto where the receiving solution was printed in the same manner as in " (1) Water resistance” above, to obtain a printing.
• MD-5 polyvinyl chloride sheet
• the printing of the ink composition was conducted in the manner the surface temperature of the recorded medium upon the impact of the ink composition became 40°C. Also, the printing was dried so as the surface temperature thereof became 80°C.
• the ink-jet recording method including the receiving solution placing step and the printing step of the present invention was an excellent ink-jet recording method.

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• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)
• Ink Jet Recording Methods And Recording Media Thereof (AREA)
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• 2016
  • 2016-11-08 EP EP16897033.3A patent/EP3461865B1/en active Active
  • 2016-11-08 CN CN201680086123.9A patent/CN109312179B/zh active Active
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  • 2016-11-08 CN CN202210804884.0A patent/CN115044248B/zh active Active
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